CN116262637A - Preparation method and application of platinum oxide nano powder - Google Patents
Preparation method and application of platinum oxide nano powder Download PDFInfo
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- CN116262637A CN116262637A CN202111545650.0A CN202111545650A CN116262637A CN 116262637 A CN116262637 A CN 116262637A CN 202111545650 A CN202111545650 A CN 202111545650A CN 116262637 A CN116262637 A CN 116262637A
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- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910003446 platinum oxide Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011858 nanopowder Substances 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 38
- 239000002244 precipitate Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- AAIMUHANAAXZIF-UHFFFAOYSA-L platinum(2+);sulfite Chemical compound [Pt+2].[O-]S([O-])=O AAIMUHANAAXZIF-UHFFFAOYSA-L 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 4
- 235000019252 potassium sulphite Nutrition 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010668 complexation reaction Methods 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- 239000003381 stabilizer Substances 0.000 abstract description 7
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 150000002484 inorganic compounds Chemical class 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 8
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 239000011943 nanocatalyst Substances 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 238000006268 reductive amination reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- -1 Platinum Metals Chemical class 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/004—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a preparation method and application of platinum oxide nano powder, which uses inorganic compound to replace macromolecule surfactant as stabilizer of nano particles, adds precursor solution containing sulfite into precursor water solution of Pt, and complexes with Pt by utilizing strong coordination of sulfite to obtain [ Pt (SO) 3 ) 3 ] 2‑ A complex, wherein the complex reacts with hydrogen peroxide to obtain platinum oxide nano powder; the method avoids adsorption poisoning of organic impurities on the surface of the powder, and has high catalyst activity; in addition, the invention has lower reaction temperature and stepsThe preparation method is simple, and can solve the problems of complex preparation process, harsh conditions and difficult batch preparation of the existing platinum oxide nano powder.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a preparation method and application of platinum oxide nano powder.
Background
The nano platinum oxide is a high-activity hydrogenation catalyst and can be used for hydrogenation or hydrogenolysis reaction of alkene, alkyne, aromatic hydrocarbon, hydroxyl, aldehyde group, imino, aromatic nitro and benzene ring. The platinum oxide catalyst has the advantages of excellent catalytic performance, high activity, high selectivity, long service life, convenient recovery and the like, and plays an important role in hydrogenation catalytic reaction in organic synthesis. In 1922 Adams et al prepared a Platinum oxide nanocatalyst by a melt decomposition reaction of chloroplatinic acid and sodium nitrate at high temperatures (reaction temperature-450 ℃), and thus the nano Platinum oxide catalyst is also commonly referred to as Adams catalyst (Platinum Metals rev.,1962,6, 150). In order to obtain a highly active platinum oxide catalyst with smaller granularity, retz et al uses betaine or a quaternary ammonium salt with a long carbon chain as a surfactant and a protective agent, and hydrolyzes platinum tetrachloride (PtCl 4) or chloroplatinic acid solution in an alkaline solution at 50 ℃ for 7 days to obtain the platinum oxide catalyst, and the platinum oxide nano catalyst prepared by the method can also be deposited on an alumina carrier to form a supported catalyst (j.am.chem.soc.1999, 121, 34, 7933). In 2004 Chen Yixian, etc., polyvinylpyrrolidone (PVP) was used as a stabilizer, and an aqueous solution of platinum tetrachloride was boiled under alkaline conditions, and acetic acid was added thereto to react for a while to obtain a platinum oxide colloid, the catalyst having a particle diameter of about 51.7nm (CN 103265085A). CN108821352a discloses a preparation method of nano platinum oxide powder, which uses a framework structure of crown ether to stabilize platinum hydroxide colloid, simultaneously uses ultrasound to convert platinum hydroxide into platinum oxide, and passivates the surface of the platinum oxide, thereby alleviating the agglomeration phenomenon of nano platinum oxide.
At present, the existing platinum oxide nano catalyst has the defects of complex preparation process, higher reaction temperature or longer reaction time, difficult large-scale amplification and higher preparation cost; in addition, the macromolecular surfactant used in the preparation process is easy to adsorb on the surface of the platinum oxide catalyst, so that the catalytic activity of the platinum oxide catalyst is affected.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a platinum oxide nano catalyst and a preparation method thereof, wherein an inorganic compound is used for replacing a macromolecular surfactant to be used as a stabilizer of nano particles, so that adsorption poisoning of organic impurities on the surface of the catalyst is avoided, and the activity of the catalyst is high; in addition, the method has the advantages of lower reaction temperature and simple steps, and can solve the problems of complex preparation process, harsh conditions and difficult batch preparation of the existing platinum oxide nano catalyst.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
the preparation method of the nano platinum oxide powder comprises the following steps:
step one, adding an aqueous solution containing sulfite ions into an aqueous solution of a Pt precursor, and carrying out complexation reaction to obtain [ Pt (SO) 3 ) 3 ] 2- A complex;
step two, adding an alkaline aqueous solution into the reaction system in the step one to adjust the pH value, so that the complex is separated out in a white precipitation form;
and thirdly, washing the white precipitate separated out in the second step, reacting with hydrogen peroxide, centrifuging, washing and drying after the reaction to obtain the nano platinum oxide powder.
Preferably, the preparation method specifically comprises the following steps:
step 1, adding a water-soluble Pt precursor into deionized water, and performing ultrasonic treatment until the Pt precursor is completely dissolved to prepare an aqueous Pt precursor solution;
step 3, slowly adding an alkaline aqueous solution into the reaction system in the step 2, and adjusting the pH of the reaction system to 8-12, wherein the reaction system gradually changes from light yellow into a colorless solution;
step 4, maintaining the pH value of the reaction system unchanged, continuously dropwise adding the aqueous solution containing sulfite ions into the colorless solution in the step 3 under the stirring condition, and stopping dropwise adding after the white precipitate is not separated out, wherein the completion of dropwise adding is ensured by continuously reacting for 1-2 hours;
step 5, washing, filtering and drying the white precipitate generated in the step 4 by using a large amount of deionized water to obtain white platinum sulfite powder;
step 6, under the stirring condition, dissolving white platinum sulfite powder into an aqueous solution, adjusting the pH value of the solution to be 1-5, adding a hydrogen peroxide aqueous solution, heating to react for 2-3 hours, cooling, and continuously adding an acidic aqueous solution to promote sedimentation of platinum oxide nano particles;
and 7, centrifugally separating the reaction solution in the step 6, washing with a large amount of deionized water, performing solid-liquid separation, and drying to obtain the platinum oxide nano powder.
Preferably, the Pt precursor in the step 1 is one or more of chloroplatinic acid, sodium chloroplatinic acid, potassium chloroplatinic acid, sodium chloroplatinic acid and platinum tetrachloride, and the Pt concentration in the Pt precursor aqueous solution is 10-50g/L.
Preferably, the slow dripping speed in the step 2 is 2-6mL/min, the stirring rotating speed is 200-1000r/min, the aqueous solution containing sulfite ions is one or more of sulfite, sodium bisulfate, potassium sulfite and potassium bisulfate aqueous solutions, and the concentration of the sulfite in the aqueous solution is 50-100g/L; when the solution turns to light yellow, the pH of the reaction system is 4-5.
Preferably, the dropping speed of the alkaline aqueous solution in the step 3 is 2-6mL/min, the stirring speed is 200-1000r/min, and the alkaline aqueous solution adopts one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide or aqueous ammonia solution.
Preferably, the pH of the reaction system in the step 4 is 7.5-11, the stirring speed is 200-1000rpm, and the reaction temperature is 0-30 ℃.
Preferably, the dilute acid solution in the step 6 is one or more of dilute sulfuric acid, dilute hydrochloric acid and acetic acid aqueous solution, the concentration is 0.05-0.5mol/L, and the pH of the reaction system is 2-4; in the step 6H 2 O 2 The molar ratio of the addition amount to the platinum sulfite is 1:1-5:1; the reaction temperature is 60-90 ℃.
Preferably, the solid-liquid separation in the step 7 is centrifugation or filtration; the drying temperature is 30-60 ℃.
The particle size of the nano platinum oxide powder prepared by the method is 1-4nm.
The nano platinum oxide powder prepared by the method can be used as a catalyst or a catalyst active component for hydrogenation reaction.
Preferably, the platinum oxide nanoparticles prepared by the present invention are supported on Al 2 O 3 On the carrier, methanol is used as solvent for reductive amination reaction of n-propylamine and benzaldehyde at room temperature and normal pressure.
The reason that the water-soluble Pt precursor is adopted in the step 1 is that the water-soluble Pt precursor is easy to prepare and low in price, the water phase synthesis is beneficial to subsequent batch amplification, the environmental pollution is small, and the preparation cost is low;
the alkaline aqueous solution was slowly added in step 3 in order to adjust the pH of the reaction system to be weakly alkaline because of [ Pt (SO) 3 ) 3 ] 2+ The complex exists in the form of ions in strong acid and strong alkaline solutions, and can be separated out from the solution in the form of white precipitate only when the pH is weak alkaline;
continuously adding sulfite solution in the step 4 ensures that precipitation is complete, ensures that 100% of Pt species in the solution are separated out of the solution and are completely converted into platinum sulfite;
in the step 5, a large amount of deionized water is adopted for washing to ensure that chloride ions are removed completely and that the catalyst is not poisoned by the chloride ions;
in step 6, H is adopted 2 O 2 Is an oxidizing agent due to H 2 O 2 After the reaction, the product is water, so that pollution to a reaction system is avoided; adding dilute acid aqueous solution after the reaction to destroy the stability of the platinum oxide colloid, and utilizing subsequent solid-liquid separation to obtain the platinum oxide nano catalyst;
the drying temperature in the step 7 is maintained at 30-60 ℃ to avoid the agglomeration phenomenon of the platinum oxide nano particles caused by high-temperature drying.
From the above description, it can be seen that the present invention has the following advantages:
1. according to the invention, the inorganic compound sulfite is used as a stabilizer of the nano particles instead of the high molecular surfactant, so that the adsorption poisoning of organic impurities on the surface of the platinum oxide powder is avoided, and the catalyst activity is high;
2. the invention can prepare the platinum oxide nano powder with small size and good dispersivity in aqueous solution without adding protective agent, and has the advantages of simple operation, mild reaction condition, environmental protection, low production cost and easy amplification synthesis.
Drawings
Fig. 1 is an XRD spectrum of the platinum oxide nanoparticle prepared in comparative example 1 of the present invention.
Fig. 2 is an XRD spectrum of the platinum oxide nanoparticle prepared in example 1 of the present invention.
Detailed Description
The invention is described in detail below with reference to examples. Unless otherwise specified, the raw materials used in the following examples and comparative examples were all commercially available conventional raw materials.
Comparative example 1: preparation of platinum oxide nano powder (without using sulfite as complexation stabilizer)
Under the condition of room temperature, 1 g of chloroplatinic acid is dispersed and dissolved in 10mL of deionized water in an ultrasonic way, 50g/L of sodium hydroxide alkaline aqueous solution is added dropwise, the dropping speed is 2 mL/min, the dropping is stopped when the pH value of a reaction system rises to 13, the reaction is continued for five days, yellow platinum hydroxide precipitation is separated out from the bottom of a container, solid powder is obtained after centrifugal separation and drying, platinum oxide powder is obtained after oxidation treatment for 1 hour at 300 ℃ in an air atmosphere, the prepared platinum oxide has large particle size and serious agglomeration through XRD characterization and TEM observation, part of platinum oxide is thermally decomposed into reduced metal Pt and oxygen through heat treatment in the air, and the catalytic performance in subsequent activity evaluation is lower.
Comparative example 2: preparation of platinum oxide nanometer powder (PVP as macromolecule stabilizer)
Under the condition of room temperature, 1 g of chloroplatinic acid and 100mg of PVP (with the molecular weight of 70000) are dispersed and dissolved in 10mL of deionized water in an ultrasonic manner, a 50g/L sodium hydroxide alkaline aqueous solution is added dropwise, the dropping speed is 2 mL/min, the dropping is stopped when the pH value of a reaction system rises to 13, after standing reaction is carried out for one day, centrifugal separation is carried out, and the mixture is dried in a vacuum oven at 60 ℃ for overnight to obtain solid powder, and platinum oxide powder is obtained after heat treatment is carried out for 1 hour in an air atmosphere at 500 ℃ (the higher temperature is adopted here to ensure that the oxidation removal of PVP, and the surface of the prepared platinum oxide particles still contains a large amount of PVP species through thermal weight, XRD characterization and TEM observation, and the platinum oxide nano particles have larger size and lower catalytic performance in subsequent activity evaluation.
Example 1
Step 1, under the condition of room temperature, 0.27 g of chloroplatinic acid is dispersed and dissolved in 10mL of deionized water in an ultrasonic manner to obtain the Pt with the concentration of 10g Pt a/L precursor solution;
step 3, maintaining the stirring speed of 300rpm, and stopping dripping when the pH value of the reaction system is regulated to be 12 by utilizing the sodium carbonate aqueous solution, wherein the color of the solution becomes colorless and a small amount of white precipitate is separated out;
step 4, continuously dropwise adding sodium bisulphite aqueous solution, increasing the precipitation amount of white precipitate, slightly reducing the pH value of the solution in the sodium bisulphite dropwise adding process, continuously supplementing and exploring the aqueous solution of sodium carbonate to maintain the pH value of a reaction system above 7.5 in the reaction process, stopping dropwise adding the sodium bisulphite solution after the white precipitate is not continuously precipitated, and continuously stirring and reacting for 1 hour under the room temperature condition;
step 5, separating the white precipitate from the supernatant by adopting a centrifugal machine, and washing the white precipitate by adopting a large amount of deionized water until the centrifugate passes through 1 mol/L AgNO 3 Detecting the chlorine ion.
Step 6, dissolving the washed white precipitate with 0.2 mol/L dilute sulfuric acid solution to obtain colorless transparent liquid, and adding excessive H 2 O 2 Aqueous solution (30 wt% H) 2 O 2 Aqueous solution, wherein H 2 O 2 The molar ratio of the catalyst to Pt is 2:1), the reaction temperature of the reaction system is controlled to be 80 ℃, a condensing tube is required to be arranged during the heating process and the reaction to prevent excessive volatilization loss of water, the reaction is continuously stirred for 3 hours, 20 milliliters of sulfuric acid solution with the molar ratio of 0.52 is added into the reaction system after the temperature is reduced, the reaction system is kept stand for 1 hour, and centrifugal separation and washing with a large amount of deionized water are carried out;
and 7, placing the solid obtained after centrifugation in a vacuum oven, drying at 40 ℃ for 4 hours, and taking out to obtain the platinum oxide nano powder.
Fig. 2 is an XRD spectrum of the prepared platinum oxide nanoparticles, which are smaller in size as seen from the extent of broadening of the corresponding XRD diffraction peaks, and which have an average grain size of about 1.0nm as calculated by using the scherrer equation.
The platinum oxide nanoparticles prepared in example 1, comparative example 1 and comparative example 2 were respectively supported on Al after being ultrasonically dispersed in an aqueous solution 2 O 3 On a carrier, ptO obtained 2 /Al 2 O 3 (5 wt%) catalyst, reductive amination of n-propylamine with benzaldehyde was examined at a substrate to Pt ratio of 1000:1 using methanol as solvent at room temperature and normal pressure, catalyst activity was measured by measuring the H absorbed per gram of Pt per minute 2 The amounts were compared. The results show that PtO prepared in example 1 2 /Al 2 O 3 Catalyst Activity (1200 mLH) 2 g -1 min -1 ) Is Al prepared in comparative examples 1 and 2 2 O 3 5 to 6 times of the catalyst (hydrogen absorption amount of comparative examples 1 and 2)200 and 180mL H respectively 2 g - 1 min -1 ) Is 6-7 times as large as the above.
Example 2
Step 1, 1.05 g of potassium chloroplatinate is dispersed and dissolved in 10mL of deionized water at room temperature to obtain a Pt concentration of 50g Pt a/L precursor solution;
step 3, maintaining the stirring speed of 300rpm, regulating the pH value of the reaction system by using sodium bicarbonate aqueous solution to rise to 12, stopping dripping, wherein the color of the solution becomes colorless and a small amount of white precipitate is separated out;
step 4, continuously dropwise adding sodium bisulphite aqueous solution, increasing the precipitation amount of white precipitate, slightly reducing the pH value of the solution in the sodium bisulphite dropwise adding process, continuously supplementing and exploring the aqueous solution of sodium carbonate to maintain the pH value of a reaction system above 8 in the reaction process, stopping dropwise adding the sodium bisulphite solution after the white precipitate is not continuously precipitated, and continuously stirring and reacting for 2 hours at room temperature;
and 5, separating the white precipitate from the supernatant by adopting a centrifugal machine, and washing the white precipitate by adopting a large amount of deionized water until the centrifugate is detected to be free of chloride ions.
Step 6, dissolving the washed white precipitate with 0.2 mol/L dilute sulfuric acid solution to obtain colorless transparent liquid, and adding excessive H 2 O 2 Aqueous solution (30 wt% H) 2 O 2 Aqueous solution, wherein H 2 O 2 The molar ratio of the catalyst to Pt is 1:1), the reaction temperature of the reaction system is controlled to be 70 ℃, a condensing tube is required to be arranged during the heating process and the reaction to prevent excessive volatilization loss of water, the reaction is continuously stirred for 5 hours, 20 milliliters of sulfuric acid solution with the molar ratio of 0.05 is added into the reaction system after the temperature is reduced, the reaction system is kept stand for 1 hour, and centrifugal separation and washing with a large amount of deionized water are carried out;
and 7, placing the solid obtained after centrifugation in a vacuum oven, drying at 50 ℃ for 6 hours, and taking out to obtain the platinum oxide nano powder.
The XRD and electron microscope characterization shows that the average particle size of the platinum oxide nano particles prepared by the steps is about 2.6 nanometers, and no obvious agglomeration phenomenon exists. The platinum oxide nano particles prepared in the example 2 are respectively carried on Al after being dispersed by water solution in an ultrasonic way 2 O 3 On a carrier, ptO obtained 2 /Al 2 O 3 (10 wt%) catalyst, the reductive amination of n-propylamine with benzaldehyde was examined at a substrate to Pt ratio of 1000:1 using methanol as solvent at room temperature and normal pressure, and the catalyst activity was compared by measuring the amount of H2 absorbed per gram of Pt per minute. The results show that PtO prepared in example 2 2 /Al 2 O 3 Catalyst Activity (1000 mLH) 2 g -1 min -1 ) Is Al prepared in comparative examples 1 and 2 2 O 3 5-6 times the catalyst (hydrogen absorption amounts of comparative examples 1 and 2 were 200 and 180mL H, respectively) 2 g - 1 min -1 ) 4-5 times of (a).
Example 3
The specific experimental procedure of this example is similar to that of example 1, except that 40g of Pt precursor was used Pt A platinum tetrachloride aqueous solution/L, a sulfite precursor solution is a potassium sulfite aqueous solution of 100g/L, wherein the dropping speed of sulfite into the Pt precursor is 5ml/min, when the solution turns from orange to light yellow, the pH is about 4.8, the stirring speed of 1500rpm is kept, the dropwise addition is stopped when the pH of the reaction system is regulated to be 12 by using a sodium hydroxide aqueous solution, and at the moment, the color of the solution turns colorless and a small amount of white precipitate is precipitated; continuously dropwise adding a potassium sulfite aqueous solution into the reaction system until the white precipitate is not increased any more; the subsequent steps are the same as in example 1.
The XRD and electron microscope characterization shows that the average particle size of the platinum oxide nano catalyst particles prepared by the steps is about 3.0 nanometers, and no obvious agglomeration phenomenon exists.
The platinum oxide nano particles prepared in the example 3 are respectively carried on Al after being dispersed by water solution in an ultrasonic way 2 O 3 On a carrier, ptO obtained 2 /Al 2 O 3 (2 wt%) catalyst at room temperatureUnder normal pressure, the reductive amination reaction of n-propylamine and benzaldehyde was examined with methanol as solvent and a substrate to Pt ratio of 1000:1, and the catalyst activity was measured by measuring the H absorbed per gram of Pt per minute 2 The amounts were compared.
The results show that PtO prepared in example 1 2 /Al 2 O 3 Catalyst Activity (800 mLH) 2 g -1 min -1 ) Is Al prepared in comparative examples 1 and 2 2 O 3 3-4 times of the catalyst (hydrogen absorption amounts of comparative examples 1 and 2 were 200 and 180mL H, respectively) 2 g -1 min -1 )。
It is to be understood that the foregoing detailed description of the invention is merely illustrative of the invention and is not limited to the embodiments of the invention. It will be understood by those of ordinary skill in the art that the present invention may be modified or substituted for elements thereof to achieve the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.
Claims (9)
1. A method for preparing platinum oxide nano-powder, which is characterized by comprising the following steps:
step one, adding an aqueous solution containing sulfite ions into an aqueous solution of a Pt precursor, and carrying out complexation reaction to obtain [ Pt (SO) 3 ) 3 ] 2- A complex;
step two, adding an alkaline aqueous solution into the reaction system in the step one to adjust the pH value, so that the complex is separated out in a white precipitation form;
and thirdly, washing the white precipitate separated out in the second step, reacting with hydrogen peroxide, centrifuging, washing and drying after the reaction to obtain the platinum oxide nano powder.
2. The preparation method according to claim 1, characterized in that it comprises in particular the following steps:
step 1, dissolving a water-soluble Pt precursor in deionized water to obtain a Pt precursor aqueous solution;
step 2, dropwise adding the aqueous solution containing sulfite ions into the Pt precursor aqueous solution, stirring at the same time, and stopping dropwise adding when the solution turns from orange to light yellow;
step 3, dropwise adding the alkaline aqueous solution into the reaction system in the step 2, stirring at the same time, and adjusting the pH of the reaction system to 8-12, wherein the reaction system is changed from light yellow to colorless;
step 4, maintaining the pH value of the reaction system unchanged, continuously dropwise adding the aqueous solution containing sulfite ions into the colorless solution in the step 3 under the stirring condition, generating white precipitate in the reaction system, stopping dropwise adding after the white precipitate is not continuously separated out, and then continuously reacting for 1-2 hours to ensure that the precipitate is complete;
step 5, washing the white precipitate generated in the step 4 with water, filtering and drying to obtain white platinum sulfite powder;
step 6, under the stirring condition, dissolving white platinum sulfite powder into an aqueous solution, adjusting the pH value of the solution to be 1-5, adding a hydrogen peroxide aqueous solution, heating to react for 2-3 hours, cooling, and continuously adding an acidic aqueous solution to promote sedimentation of platinum oxide nano particles;
and 7, centrifugally separating the reaction liquid in the step 6, washing with deionized water, performing solid-liquid separation, and drying to obtain the platinum oxide nano powder.
3. The method according to claim 2, wherein in the step 1, the Pt precursor is one or more of chloroplatinic acid, sodium chloroplatinic acid, potassium chloroplatinic acid, sodium chloroplatinic acid, and platinum tetrachloride, and the Pt concentration in the Pt precursor aqueous solution is 10 to 50g/L.
4. The preparation method according to claim 2, wherein in the step 2, the dropping speed is 2-6mL/min, the stirring speed is 200-1000r/min, the aqueous solution containing sulfite ions is one or more of sulfite, sodium bisulfate, potassium sulfite and potassium bisulfate aqueous solution, and the concentration of sulfite in the aqueous solution containing sulfite ions is 50-100g/L; when the solution turns to light yellow, the pH of the reaction system is 4-5.
5. The preparation method according to claim 2, wherein in the step 3, the dropping speed is 2-6mL/min, the stirring speed is 200-1000r/min, and the alkaline aqueous solution is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonia water and potassium hydroxide aqueous solution; in the step 4, the pH value of the reaction system is 7.5-11, the stirring speed is 200-1000rpm, and the reaction temperature is 0-30 ℃.
6. The preparation method according to claim 2, wherein in the step 6, the acidic aqueous solution is one or more of dilute sulfuric acid, dilute hydrochloric acid and acetic acid aqueous solution, and the concentration of the acidic aqueous solution is 0.05-0.5mol/L; h 2 O 2 The molar ratio of the addition amount to the platinum sulfite is 1:1-5:1; the reaction temperature is 60-90 ℃; in the step 7, the solid-liquid separation mode is centrifugation or filtration; the drying temperature is 30-60 ℃.
7. A platinum oxide nanopowder prepared by the method of any one of claims 1-6.
8. The platinum oxide nanopowder according to claim 7, wherein the platinum oxide nanopowder has a particle size of 1-4nm.
9. Use of the platinum oxide nano-powder according to claim 7 as a catalyst or a catalyst active component in hydrogenation reactions.
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